CN1060186C - 复合材料，其制造方法及其用途 - Google Patents

复合材料，其制造方法及其用途 Download PDF

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Publication number
CN1060186C
CN1060186C CN94113856A CN94113856A CN1060186C CN 1060186 C CN1060186 C CN 1060186C CN 94113856 A CN94113856 A CN 94113856A CN 94113856 A CN94113856 A CN 94113856A CN 1060186 C CN1060186 C CN 1060186C
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Prior art keywords
tpv
thermoplastic
segmented copolymer
matrix material
elastomerics
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Expired - Fee Related
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CN94113856A
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English (en)
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CN1109896A (zh
Inventor
M·赫特
P·阿列克斯
M·塞夫
C·杜松
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Arkema France SA
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Elf Atochem SA
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Abstract

本发明复合材料包括与热塑性材料结合的橡胶/热塑性材料掺混物，而该掺混物形式为含有在官能化并在与热塑性材料混合期间硫化的橡胶瘤状体的热塑性基质形式。
本发明还包括在热塑性材料上复制硫化的橡胶/热塑性材料掺混物而得到的复合材料制品。

Description

复合材料，其制造方法及其用途
本发明涉及复合材料制品，其中包括热塑性材料，而该热塑性材料本身又与特殊的一类热塑性弹性体结合，这些热塑性弹性体是通过以细粒形式分散在热塑性基质中的橡胶经动态硫化的方法而得到的(下称TPV)，即本发明制品包括热塑性材料和TPV，其中TPV也称为橡胶／热塑性材料掺混物。
欲制成满足各种条件的工业制品，已越来越需要将机械和理化性能范围尽可能宽的材料组合起来。本发明即涉及不借助粘合剂而是采用已众所周知的操作方法如复制模型，双材料注塑，共同挤出等方法组合起来的复合材料。
欧洲专利申请EP 550346提出了硫化橡胶和聚酰胺嵌段共聚物制备方法及这两者不用粘合剂而组合起来的制品。在同一物品中，该方法可将橡胶的特殊性能(残留的受压变形量小，硬度低，具有耐磨性，抗热油性……)和聚醚－酯－酰胺的特殊性能(柔软，机械性能高，具有疲劳强度……)结合起来。
但是，用来达到这些目的的方法部分也是橡胶工业方法，其特点是周期长(一般为10分钟)并且操作费用高。
本发明目的是制造具有上述各种功能的复合材料制品，其中用热塑性橡胶即TPV代替硫化橡胶构成的部分并且其中采用热塑性材料加工方法。众所周知，TPV为性能极其接近于硫化橡胶的材料，同时又完全保留了应用热塑性材料的加工灵活性(参见A．Coran etal．he“Thermoplastic Elastomers”，Mac Millan Publishing 1987中说明这类材料的综述论文)。
欧洲专利EP 231674说明了由聚酰胺嵌段共聚物和非官能化腈橡胶构成的掺混物。
日本专利申请JP 63－81158说明了基于聚醚酯酰胺和至少部分交联的的各种橡胶的组合物，其中两种组分比例为1∶1。
但在本发明中，橡胶硫化的优点在于，即使主要组分为橡胶，也可得到热塑性基质。优越性还在于具有由其中已分散了硫化橡胶的热塑性基质形成的TPV。即使在热塑性材料为少数，而橡胶为多数的情况下，也是如此。
在由该日本专利申请人提供的实施例中，只有橡胶的部分硫化，而进一步硫化(50－90％)可提高其性能如断裂强度，耐磨性，韧性和残留受压变形性均更好。
用于制造本发明复合材料制品的TPV包括：
至少一种可硫化的官能化弹性体；
至少一种聚醚或非晶形聚酯嵌段共聚物。
已发现这些TPV组合物可通过共同注塑，复制模型，共同挤出等方法，即基本上不用粘合剂与各种热塑性材料结合。
这两种材料间界面处的结合强度一般都高于两种材料中每一种的断裂强度。不过，在全部或部分接触表面上加粘合剂也不会偏离本
发明范围。
可硫化的弹性体量可为TPV，即可硫化弹性体／嵌段共聚物组合物的20－90wt％(重量百分比)。
至于构成TPV的嵌段共聚物，其聚醚或非晶形聚酯嵌段构成其挠性或柔性部分，而聚酰胺，聚酯或聚氨酯半晶形嵌段构成其刚性部分。
作为举例，可举出非晶形聚酯二醇与多异氰酸酯反应形成的聚醚氨酯以及聚醚二醇与多异氰酸酯反应形成的聚醚氨酯。
嵌段共聚物可包括聚醚单元和聚酯单元。这些单元例如为聚醚嵌段和聚酯嵌段。这些产品的已知名称为聚酯弹性体并且是热塑性材料。
聚醚为例如聚乙二醇(PEG)，聚丙二醇(PPG)或聚丁二醇(PTMG)。
这些聚醚的分子量 可为250-6000。
这些聚醚可与至少一种二羧酸缩合而形成聚酯弹性体的柔性或挠性嵌段。
这些聚酯嵌段例如可通过至少一种二醇与至少一种二羧酸缩合而得到。二醇可为乙二醇，丙二醇或丁二醇。二酸可为对苯二甲酸。这些嵌段构成聚酯弹性体的刚性嵌段。
这些刚性嵌段可包括大量由聚醚与二酸反应所形成的单元。这些刚性嵌段和柔性嵌段由酯键连接起来。这些聚酯弹性体可见于EP402883和EP 405227。
至于含有聚醚单元和酰胺单元的嵌段共聚物，这些单元可按无规或有序方式分布。酰胺单元可在二胺与二酸反应或α，ω-氨基羧酸缩合形成的低聚物中孤立存在或分组存在。
最广泛应用的弹性体为包括聚酰胺嵌段和聚醚嵌段的弹性体。聚酰胺嵌段可由内酰胺或α，ω-氨基酸缩合或由二酸和二胺反应而形成。
这些聚酰胺嵌段可在二酸存在下得到。可得到带有羧酸端基的聚酰胺嵌段。这些聚酰胺嵌段的分子量
Figure 9411385600052
为600-5000。
聚醚可为例如聚乙二醇，聚丙二醇或聚丁二醇，其分子量
Figure 9411385600053
为250-6000，大量的聚醚可按顺序连接起来，如在聚醚二醇的情况下用二酸连接起来。这些聚酰胺嵌段和这些聚醚二醇嵌段的缩合可生成聚醚酯酰胺。
应用含聚酰胺嵌段和聚醚嵌段的其它弹性体亦不会偏离本发明范围。这些产品可通过内酰胺或α，ω－氨基酸，二酸和聚醚二醇或聚醚二胺反应而得到。也可将含胺端基的聚酰胺嵌段与聚醚二酸缩合并可将含酸端基的聚酰胺嵌段与聚醚二胺(后者称为聚醚酰胺)缩合。
所有这些产品已见于US 4，331，786，4，115，475，4，195，015，4，839，441和4，864，014。
在TPV中存在的弹性体在掺混期间用选自过氧化物，硫及其加速剂和硫供体分子的硫化体系交联。
宜于生产本发明TPV掺混物的可硫化的合成或天然弹性体对本技术领域的技术人员而言已众所周知，其中本发明定义中的弹性体指其由许多弹性体混合物构成。
这些弹性体或弹性体混合物硫化后100℃下的残留受压变形量(DRC)小于50％，一般为5－40％，优选小于30％。
这种弹性体可用例如羧酸，酸酐，该羧酸盐或酯基团或用环氧基或氨基或用卤素官能化。
本发明还涉及TPV制造方法，其中混合以下物料：
已事先用足够量硫化剂及任选的填料和增塑剂配制成的可硫化官能化弹性体；
嵌段共聚物；
混合温度足以使嵌段共聚物熔化并引起硫化，而其焦烧(grillage)时间又足够长以防止在将弹性体充分分散在熔融嵌段共聚物中之前消耗掉弹性体中的所有官能团。
作为弹性体例子，可以举出天然橡胶，聚异戊二烯，基于苯乙烯／丁二烯共聚物的聚合乳液，基于苯乙烯／丁二烯共聚物的聚合溶液，用镍、钴、钛或钕催化所得顺式位置双键数量大的聚丁二烯，卤代乙烯／丙烯／二烯三聚物，卤代丁基橡胶，苯乙烯／丁二烯嵌段共聚物，苯乙烯／异戊二烯嵌段共聚物，上述聚合物的卤代产物，丙烯腈／丁二烯共聚物，氢化丙烯腈／丁二烯共聚物，丙烯酸弹性体，含氟弹性体，氯丁二烯和表氯醇橡胶。
未被官能化的上述弹性体可例如按已知方式用基团接枝或通过与已官能化的弹性体如丙烯酸弹性体或羧化NBR(X－NBR)混合而官能化。
在上述弹性体中，可有效选用以下弹性体：羧化腈弹性体，丙烯酸弹性体，羧化聚丁二烯，接枝乙烯／丙烯／二烯三聚物或这些聚合物与相同但未接枝弹性体如腈橡胶，聚丁二烯，乙烯／丙烯／二烯三聚物单独或其混合物的混合物。
上述弹性体也可与无官能团的橡胶混合，官能化的弹性体可保证后者与嵌段共聚物之间的相容性。
也可加入已硫化橡胶(粉碎物料循环)。上述可硫化的弹性体包括的官能团重量以所述弹性体计优选为0．3－10％。
用于生产这些TPV的硫化体系对本技术领域的技术人员而言已众所周知，因此本发明并不仅限于特殊的硫化体系。只是这些体系应满足本发明上述定义中确定的硫化动力学所涉及的标准。
在弹性体基于不饱和单体(丁二烯，异戊二烯，亚乙烯基降冰片烯等)时，就可举出以下四类硫化体系：
硫体系，其中包括硫及与其并用的促进剂如二硫代氨基甲酸金属盐(二甲基二硫代氨基甲酸锌，碲等……)，秋兰姆二硫化物(四甲基秋兰姆二硫化物等……)，硫酰胺等。
这些体系也可含氧化锌并可与硬脂酸并用。
硫供体体系，其中用于桥连的大部分硫来自于含硫分子如上述有机硫化合物。
含酚醛树脂的体系，其中包括可被卤代的双官能酚醛树脂并混用促进剂如氯化亚锡或氧化锌。
过氧化物体系，用这些体系可以制成热稳定性更高，呈白色，而不是黄色的产品，这与硫供体体系的情形相同。任何可提供自由基的体系(二枯基过氧化物等……)可与氧化锌和硬脂酸并用。
在弹性体为丙烯酸弹性体(带酸或环氧官能团或其它任何可交联的活性官能团的聚丙烯酸丁酯)时，可用常见交联剂如基于二胺(邻甲苯氨基胍，联苯基胍等……)或受保护二胺(六亚甲基二胺氨基甲酸盐等……)的交联剂。
弹性组合物中可通过加入填料如炭黑，二氧化硅，高岭土，粘土，滑石，白垩等而达到某些特殊的性能(如提高机械性能)。优选将钙化高岭土加入二氧化硅中以避免在与橡胶掺混期间熔融态的热塑性材料部分水解。这些填料可用硅烷，聚乙二醇或任何其它偶合分子进行表面处理。一般来说，填料量为5－100重量份／100份弹性体。
另外，这些组合物可用增塑剂软化，这些增塑剂例如为源自石油的矿物油，苯二甲酸酯或癸二酸酯，液态聚合物增塑剂如任选羧化低分子量聚丁二烯及本技术领域的技术人员众所周知的其它增塑剂。
用于实施该方法的硫化剂混合物应使其必须按动力学要求达到弹性体完全交联，从而获得如本发明定义中提到的良好抗分离性及普遍获得良好的橡胶性能(100℃下残留受压变形量，抗拉强度等……)。
有利的是，借助振动流变仪测定的动力学是使160℃下90％硫化的特征时间t90不超过15分钟，优选5－10分钟。
在羧化不饱和弹性体情况下，由于分散在热塑性基质中的橡胶相硫化是通过双键和羧基发生的，所以须阻止更具活性的后者为达到交联的目的而完全用光，因为要达到与热塑性材料的相容性仍需要这些基团。这就是为什么须适当控制硫化温度以达到足够长的焦烧时间并因而使仍是自由的羧基有时间与熔融相中的热塑性材料反应的原因。
本发明还涉及含官能化橡胶瘤状体的热塑性基质，热塑性材料选自上述针对TPV时提及的热塑性材料。
上述TPV可与热塑性材料并用，这些热塑性材料选自例如聚酰胺，含聚酰胺嵌段的热塑性弹性体，含聚酯嵌段的热塑性弹性体，半晶形聚酯，聚氨酯(TPU)和刚性或增塑的PVC。可应用对本技术领域的技术人员而言众所周知的方法如复制模型，共同注塑，共同挤出叠层等方法将其结合起来。
结合或组合应用的典型例子，可举出：
用复制模型或共同注塑法得到鞋制品
用聚醚酯酰胺制成鞋底，其中选用该材料是因为其疲劳强度高，变形滞后量小并且冷性能优良，其表面上注塑覆盖TPV掺混物以形成耐磨，抗滑，耐油脂的面层或耐磨层。
共同挤出型材
某些上述TPV可与增塑PVC组合用于制成受压型材零部件，这些型材要求有优良的加热时抗蠕变强度，高柔性或挠性，适宜于在建筑和汽车中作为密封件应用。
共同挤出管材
这些TPV可挤出制成加热时具有优良抗油性的柔性或挠性管。采用共同挤出法，可对具有外层的管加覆盖层，其中该外层为上述热塑性材料之一如聚酰胺。
运输带
在现有的各种多层结构中，有一些结构的外层由橡胶与共聚醚酯酰胺，TPV或含聚酯或TPU嵌段的共聚醚表面结合而构成。这些结合的橡胶层可有利地用与一或多种上述热塑性材料一起共同挤出的上述TPV代替。
用TPV达到耐磨性，高摩擦系数，弹性和低硬度，而热塑性材料则耐折叠疲劳强度，疲劳强度和韧性。
传送带
有些带要求极具柔性或挠性的材料以便完全包覆以高速转动的小直径轮。与该轮接触的面必须具有类似橡胶的优良滑动弹性及高摩擦系数。
实施例1，2，3和4涉及如实施例5－7所述可制成复合材料制品的TPV生产方法及其特点。
实施例1
a)按以下方式(重量份)用密闭式混合机于不超过120℃的温度下配制商标为CHEMIGUM(Goodyear的R．M．)的羧化腈弹性体(XNBR)。
羧化丁二烯／丙烯腈     XNBR    RCG     7343∶110
二氧化硅              KS      300         ∶20
邻苯二甲酸二异壬酯     DINP                ∶5
聚乙二醇              PEG     4000         ∶2
氧化钛               TiO2               ∶5
乙烯基硅烷(三甲氧基)   SI      69           ∶1
抗氧化剂              WINGSTAY29           ∶1
活化剂                POLYVESTC70          ∶4
硫                                         ∶1．8
ZnO                                       ∶ 5
硬脂酸                                     ∶1
苯并噻唑基二硫化物     MBTS                 ∶1．5
四甲基秋兰姆二硫化物   TMTD                 ∶0．5
然后用密闭式混合机将该弹性体组合物按下列组成比与ShoreD硬度为40的商标为PEBAX 4033的聚醚酯酰胺混合，其中所说聚醚酯酰胺包括聚丁二醇嵌段和PA 12嵌段：
弹性体       60％
PEBAX 4033   40％
混合结束时的温度为220℃。
这种TPV在挤出机中造粒后用热塑性材料压制机经注射模塑成型而制成各种试件模制品。
按所述标准测定的性能试验列在下表1中。
b)用已预研磨的CHEMIGUM NX 775产品(Goodyear的R．M．，含7％羧基)试验得到类似结果。
实施例2
用密闭式混合机将实施例1的弹性体组合物与商标为HYTREL 4056的含聚酯嵌段的聚醚(PBT嵌段和对苯二甲酸PTMG嵌段)按下列组成比混合：
弹性体    60％
HYTREL    40％
混合结束时温度为210℃。
该掺混物的性能列在表1中。
实施例3
用密闭式混合机将实施例1的弹性体组合物与商标为DESMOPAN 590的含聚酯嵌段的聚氨酯按下列组成比混合：
弹性体         60％
DESMOPAN       40％
混合结束时温度为230℃。
该掺混物的性能列在表1中。
实施例4
用密闭式混合机在不超过120℃的温度下生产弹性体，填料，增塑剂和硫化体系的混合物。该混合物组成如下：
CHEMIGUM丁二烯－腈弹性体P90                  ∶70
羧化丁二烯－腈弹性体    CHEMIGUM  RCG 7343   ∶30
二氧化硅               KS 300               ∶10
邻苯二甲酸异壬酯        DINP                 ∶20
氧化锌                ZnO                 ∶5
氧化钛                TiO2               ∶5
硅烷                   SI 69                ∶2
蜡                     PEG 4000             ∶2
硬脂酸                                      ∶0．5
trigomox               B过氧化物            ∶2
丙烯酸锌                                    ∶2
用密闭式混合机将该弹性体组合物与Shore D硬度为55的商标为PEBAX 5533的聚醚酯酰胺按下列组成比混合其中聚醚酯酰胺包括PA 12和PTMG嵌段：
弹性体        70％
PEBAX 5533    30％
混合结束时温度为210℃。
该掺混物的性能列在表1中。
实施例5
商标为KRAUS MAFFEI并且夹持力为110T(1100kN)的热塑性材料注射模塑成型压制机中装有尺寸为100×100×5mm的模具。
预先经过注射模塑成型方法制成尺寸为100×100×2mm的各种聚醚酯酰胺和PA 12板。将这些板作为塞子放在厚度为5mm的模具中。用实施例1的TPV热塑性橡胶复制模型，其中采用了如下所列的各系列板：
5．1：商标为PEBAX 4033的聚醚酯酰胺板
5．2：商标为PEBAX 5533的聚醚酯酰胺板
5．3：商标为PEBAX 6333的聚醚酯酰胺板除Shove D硬度为63而外，与PEBAX 4033相同5．4：商标为Rilsan AESNO的聚酰胺12板
注塑物料温度为260℃，而模具温度为40℃。在例5．4情况下，注塑温度为290℃。
50mm／mn速度下两种材料间的剥离力列在下表中。
例        5．1    5．2    5．3    5．4
剥离力    5．6    7．5    7．6    7．0
在所有情况下，热塑性材料中断裂处显示本质上原来是结合的。
实施例6
在实施例5的条件下用实施例2的TPV复制商标为HYTREL4056的含聚酯嵌段的聚醚板。
两种材料间的剥离强度为6．2daN／cm。
实施例7
在实施例5的条件下用实施例3的TPV复制商标为DESMOPAN 590的聚氨酯板。两种材料间的剥离强度为5．2daN／cm，并且断裂处显示TPV原来是结合的。
表1
    实施例     1     2     3     4
    性能     方法 单位     822714.93776.28.811.55415993.4     792514.55204.56.58.756.856     772513.13205.48.612.739.146.5   8530未测定未测定未测定未测定未测定未测定48100
  硬度断裂强度断裂伸长模数100％200％300％未划线撕裂100℃下22小时的残留受压变形量磨损 ASTMD2240ASTMD412ASTMD624ASTMD395DlN 53516  ShoreAShoreDMpa％Mpakn/m％mg/mm3
 ASTMn°3油溶胀 ASTMD471 ％Vol 16 未测定 未测定 2.6

Claims (7)

1．复合材料，其中包括热塑性橡胶掺混物(TPV)，而该热塑性橡胶掺混物本身又在基本上不用粘合剂的情况下与热塑性材料结合，所述TPV包括(ⅰ)至少一种可硫化的官能化弹性体和(ⅱ)至少一种含聚醚或非晶形聚酯嵌段的嵌段共聚物。
2．权利要求1的复合材料，其特征在于TPV中的嵌段共聚物包括构成其柔性部分的聚醚或非晶形聚酯嵌段及构成其刚性部分的聚酰胺，聚酯或聚氨酯嵌段。
3．权利要求1或2的复合材料制造方法，其特征在于TPV和热塑性材料用共同注塑法，复制模型法或共同挤出法结合起来，其中混合以下物料：
已事先用足够量硫化剂及任选的填料和增塑剂配制成的可硫化官能化弹性体；
嵌段共聚物；
混合温度足以使嵌段共聚物熔化并引起硫化，而其焦烧时间又足够长以防止在将弹性体充分分散在熔融嵌段共聚物中之前消耗掉弹性体中的所有官能团。
4．鞋底，其中包括权利要求1或2的复合材料。
5．共同挤出型材，其中包括权利要求1或2的复合材料。
6．运输带，其中包括权利要求1或2的复合材料。
7．传送带，其中包括权利要求1或2的复合材料。
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US5637407A (en) 1997-06-10
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